CN102074737B - Electrolyte for lithium battery and lithium battery containing the same - Google Patents
Electrolyte for lithium battery and lithium battery containing the same Download PDFInfo
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- CN102074737B CN102074737B CN201010558114.XA CN201010558114A CN102074737B CN 102074737 B CN102074737 B CN 102074737B CN 201010558114 A CN201010558114 A CN 201010558114A CN 102074737 B CN102074737 B CN 102074737B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
- H01M2300/0028—Organic electrolyte characterised by the solvent
- H01M2300/0034—Fluorinated solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to an electrolyte for lithium batteries and a lithium battery containing the electrolyte. The electrolyte for lithium batteries comprises: a non-aqueous organic solvent, a lithium salt, a first compound represented in formula 1, and a second compound represented in formula 2, wherein Q1, Q2, and R1-R6 are as defined in the description.
Description
The cross reference of related application
This application claims priority and the rights and interests of the korean patent application No.10-2009-0112197 that on November 19th, 2009 submits in Korean Intellectual Property Office, the full content of this application is incorporated herein by reference.
Technical field
Below describe relate to for lithium battery electrolyte and comprise this electrolytical lithium battery.
Background technology
Lithium battery is the one of the battery of electric energy by the chemical energy that the electrochemical redox reaction by chemical substance produces, and it comprises positive pole, negative pole and electrolyte.
Lithium battery can be used as the power supply of various suitable electronic device, and wherein said electronic equipment can be used in various proper environment.Such as, described electronic equipment can use in hot environment or near burning things which may cause a fire disaster.Therefore, even if need exploitation not only at room temperature to use but also at high temperature or also can keep electrical characteristics such as high power capacity and high-output power and keep the lithium battery of stability when burning things which may cause a fire disaster uses.
Summary of the invention
An aspect of embodiment of the present invention relates to the highly non-flame properties electrolyte for lithium battery.
An aspect of embodiment of the present invention relates to and comprises the non-flame properties electrolytical lithium battery of described height.
Other aspect will be partly articulated in the following description, and will be partly distinct from described description, or know by the practice of presented execution mode.
According to one or more execution mode of the present invention, the electrolyte for lithium battery comprises: non-aqueous organic solvent, lithium salts, the first compound represented by following formula 1 and the second compound represented by following formula 2:
Formula 1
Q
1-O-Q
2
Formula 2
Wherein,
Q1 is the C replaced by one or more-F
2-C
30alkyl;
Q
2for C
1-C
30alkyl, C
2-C
30thiazolinyl, C
2-C
30alkynyl, the C replaced by one or more-F
1-C
30alkyl, the C replaced by one or more-F
2-C
30thiazolinyl or the C replaced by one or more-F
2-C
30alkynyl;
R in described second compound
1~ R
6be selected from-F and-OT independently of one another
1, wherein T
1for: C
1-C
30alkyl; C
2-C
30thiazolinyl; C
2-C
30alkynyl; C
6-C
12cycloalkyl; C
6-C
30aryl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
1-C
30alkyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
30thiazolinyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
30alkynyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
12cycloalkyl; Or the C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
30aryl, wherein gets rid of wherein R
1~ R
6be all-F or-OT
1situation, and the number ratio of fluorine atom in described first compound and hydrogen atom is 1 or higher.
According to one or more execution mode of the present invention, lithium battery comprises: the negative pole comprising negative active core-shell material; Comprise the positive pole of positive electrode active materials; With above-mentioned electrolyte.
Accompanying drawing explanation
Following description from the execution mode considered by reference to the accompanying drawings is become distinct and is more readily understood by these and/or other side, wherein:
Fig. 1 is the perspective schematic view of the lithium battery according to embodiment of the present invention;
Fig. 2 is the figure of display to the result that the gas chromatography/mass spectrometry (GC/MS) of the compound 1a used in Evaluation operation example is analyzed;
Fig. 3 is the figure of display to the result that the GC/MS of the compound 2a used in Evaluation operation example analyzes;
Fig. 4 is the figure of display to the result that the GC/MS of the compound 2b used in Evaluation operation example analyzes;
Fig. 5 A and 5B is the figure of display to the result that the electrolytical GC/MS that the lithium battery of embodiment 1 comprises analyzes;
Fig. 6 A and 6B is the figure of display to the result that the electrolytical GC/MS that the lithium battery of embodiment 2 comprises analyzes;
Fig. 7 A and 7B is the figure of display to the result that the electrolytical GC/MS that the lithium battery of embodiment 4 comprises analyzes; With
Fig. 8 A and 8B is the figure of display to the result that the electrolytical GC/MS that the lithium battery of embodiment 5 comprises analyzes.
Embodiment
To mention each execution mode in detail now, the example is shown in the drawings, and wherein identical Reference numeral represents identical element all the time.In this, embodiment of the present invention can have multi-form and should not be construed as and be limited to carried out description herein.Therefore, execution mode is described, to explain each side of this specification by means of only with reference to accompanying drawing below.
According to an embodiment of the invention, the electrolyte for lithium battery comprises: non-aqueous organic solvent, lithium salts, the first compound represented by following formula 1 and the second compound represented by following formula 2:
Formula 1
Q
1-O-Q
2
Formula 2
Described first compound has relatively high noninflammability and relative low reduction-decomposition reaction, and therefore can keep or improve the electrical characteristics of lithium battery.
Q in described first compound
1for the C replaced by one or more-F (fluorine)
2-C
30alkyl.
Such as, the Q in described first compound
1can be by the C of the straight or branched of one or more-F replacement
2-C
20alkyl.Or, the Q in described first compound
1can be by the C of the straight or branched of one or more-F replacement
2-C
10alkyl.But, the present invention is not limited thereto.
Q in described first compound
2can be the C of straight or branched
2-C
20alkyl or the C of straight or branched replaced by one or more-F
2-C
20alkyl.In addition, the Q in described first compound
1can be the C of straight or branched
2-C
10alkyl or can be the C of the straight or branched replaced by one or more-F
2-C
10alkyl.But, the present invention is not limited thereto.
Q in described first compound
1and Q
2can be by the methyl of one or more-F replacement, by the ethyl of one or more-F replacement, by the propyl group of one or more-F replacement, by the butyl of one or more-F replacement, by the amyl group of one or more-F replacement, by the hexyl of one or more-F replacement, by the heptyl of one or more-F replacement or by the octyl group of one or more-F replacement independently of one another, but be not limited thereto.
Q in described first compound
1and Q
2-CF can be selected from independently of one another
2-CF
2h ,-CH
2-CF
2-CF
2h ,-CF
2-CF
3,-CH
2-CF
2-CF
3,-CF
2-CFH
2, and-CH
2-CF
2-CFH
2, but be not limited thereto.
Fluorine atom in described first compound and the number ratio of hydrogen atom can be about 1 or higher and (or are not less than 1; Or about 1 or larger), such as, about 1 ~ about 20 (or 1 ~ 20).Fluorine atom in described first compound and the number ratio of hydrogen atom can be about 1 ~ about 10 (or 1 ~ 10), such as, and about 1 ~ about 5 (or 1 ~ 5), but be not limited thereto.Fluorine atom in described first compound and the number ratio of hydrogen atom can be about 1 (or 1), about 1.5 (or 1.5), about 2 (or 2), about 2.5 (or 2.5), about 3 (or 3), about 3.5 (or 3.5) or about 4 (or 4), but are not limited thereto.If the fluorine atom in described first compound and the number ratio of hydrogen atom are in above-mentioned scope, then described first compound can have relatively high noninflammability.
Described second compound can be the noninflammability that electrolyte provides relatively high.
R in described second compound
1~ R
6-F and-OT can be selected from independently of one another
1.T
1can be: C
1-C
30alkyl; C
2-C
30thiazolinyl; C
2-C
30alkynyl; C
6-C
12cycloalkyl; C
6-C
30aryl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
1-C
30alkyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
30thiazolinyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
30alkynyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
12cycloalkyl; Or the C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
30aryl.
R in described second compound
1~ R
6as defined above.But, get rid of wherein R
1~ R
6be all-F or-OT
1situation.
Such as, in described second compound, R
1~ R
5can be-F and R
6can be-OT
1; Or in described second compound, R
1, R
2, R
4and R
5can be-F and R
3and R
6can be-OT
1.
In above second compound, T
1can be: C
1-C
20alkyl; C
2-C
20thiazolinyl; C
2-C
20alkynyl; C
6-C
12cycloalkyl; C
6-C
20aryl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
1-C
20alkyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
20thiazolinyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
20alkynyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
12cycloalkyl; Or the C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
20aryl.
Such as, the T in described second compound
1can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, acetenyl, cyclohexyl, phenyl, pentalene base, indenyl, naphthyl, Azulene base, heptalene base, indacene base, acenaphthenyl, fluorenyl, that thiazolinyl non-, phenanthryl, anthryl, fluoranthene base, Sanya phenyl, pyrenyl,
base, aphthacene base, Pi base, perylene base, pentacene base, hexacene base, by the methyl that one or more-F replaces, by the ethyl that one or more-F replaces, by the propyl group that one or more-F replaces, by the butyl that one or more-F replaces, by the amyl group that one or more-F replaces, by the hexyl that one or more-F replaces, by the heptyl that one or more-F replaces, by the octyl group that one or more-F replaces, by the vinyl that one or more-F replaces, by the acrylic that one or more-F replaces, by the cyclobutenyl that one or more-F replaces, by the pentenyl that one or more-F replaces, by the hexenyl that one or more-F replaces, by the heptenyl that one or more-F replaces, by the octenyl that one or more-F replaces, by the acetenyl that one or more-F replaces, by the cyclohexyl that one or more-F replaces, by the phenyl that one or more-F replaces, by the pentalene base that one or more-F replaces, by the indenyl that one or more-F replaces, by the naphthyl that one or more-F replaces, by the Azulene base that one or more-F replaces, by the heptalene base that one or more-F replaces, by the indacene base that one or more-F replaces, by the acenaphthenyl that one or more-F replaces, by the fluorenyl that one or more-F replaces, by that thiazolinyl non-that one or more-F replaces, by the phenanthryl that one or more-F replaces, by the anthryl that one or more-F replaces, by the fluoranthene base that one or more-F replaces, by the Sanya phenyl that one or more-F replaces, by the pyrenyl that one or more-F replaces, replaced by one or more-F
base, the aphthacene base replaced by one or more-F, the pentacene base being replaced Pi base by one or more-F, replaced perylene base by one or more-F, replaced by one or more-F or the hexacene base replaced by one or more-F.But, the present invention is not limited thereto.
T in described second compound
1can be C
1-C
10alkyl, C
2-C
10thiazolinyl, C
6-C
14aryl, the C replaced by one or more-F
1-C
10alkyl, the C replaced by one or more-F
2-C
10thiazolinyl or the C replaced by one or more-F
6-C
14aryl, but be not limited thereto.
T in described second compound
1can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, vinyl, acrylic, cyclobutenyl, pentenyl, hexenyl, heptenyl, octenyl, phenyl, naphthyl, fluorenyl, by the methyl that one or more-F replaces, by the ethyl that one or more-F replaces, by the propyl group that one or more-F replaces, by the butyl that one or more-F replaces, by the amyl group that one or more-F replaces, by the hexyl that one or more-F replaces, by the heptyl that one or more-F replaces, by the octyl group that one or more-F replaces, by the vinyl that one or more-F replaces, by the acrylic that one or more-F replaces, by the cyclobutenyl that one or more-F replaces, by the pentenyl that one or more-F replaces, by the hexenyl that one or more-F replaces, by the heptenyl that one or more-F replaces, by the octenyl that one or more-F replaces, by the phenyl that one or more-F replaces, by the naphthyl that one or more-F replaces, or by the fluorenyl that one or more-F replaces, but be not limited thereto.
T
1can be methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, the methyl replaced by one or more-F, the ethyl replaced by one or more-F, the propyl group replaced by one or more-F, the butyl replaced by one or more-F, the amyl group replaced by one or more-F, the hexyl replaced by one or more-F, the heptyl replaced by one or more-F or the octyl group replaced by one or more-F, but be not limited thereto.
The amount of described first compound can be about 10 parts by volume ~ about 30 parts by volume (or 10 parts by volume ~ 30 parts by volume), based on the cumulative volume of the non-aqueous organic solvent of 100 parts by volume, the first compound and the second compound.The amount of described first compound can be about 20 parts by volume ~ about 30 parts by volume (or 20 parts by volume ~ 30 parts by volume), such as about 20 parts by volume ~ about 25 parts by volume (or 20 parts by volume ~ 25 parts by volume), based on the cumulative volume of the non-aqueous organic solvent of 100 parts by volume, the first compound and the second compound.The amount of described second compound can be about 5 parts by volume ~ about 10 parts by volume (or 5 parts by volume ~ 10 parts by volume), based on the cumulative volume of the non-aqueous organic solvent of 100 parts by volume, the first compound and the second compound.If the amount of the amount of described first compound and described second compound in above-mentioned scope, then can obtain relatively high noninflammability, and not have the remarkable reduction of electrolytical viscosity and ionic conductivity.
Non-aqueous organic solvent contained in electrolyte can play the effect of the migration medium of the ion related in the electrochemical reaction of lithium battery.
The example of described non-aqueous organic solvent can comprise carbonate solvent, ester solvent, ether solvents, ketone solvent, alcoholic solvent and aprotic solvent.
The example of described carbonate solvent can comprise carbonate material, comprising: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonic acid ester (EPC), methyl ethyl carbonate (EMC), ethylene carbonate (EC), propene carbonate (PC) and butylene (BC); And the derivative that their wherein at least one hydrogen atom is replaced by-F.Described derivative can comprise the carbonic acid PVF ester (FEC) by replacing the hydrogen of EC to obtain with-F, but is not limited thereto.The compound 3 represented by following formula 3 can be used as carbonate solvent, but is not limited thereto: formula 3
Z
1-O-C(＝O)-Z
2
Z in formula 3
1and Z
2can be C independently of one another
1-C
10alkyl or the C replaced by one or more-F
1-C
10alkyl.
Such as, the Z in formula 3
1and Z
2can be methyl independently of one another, ethyl, propyl group, butyl, amyl group, hexyl, the methyl replaced by one or more-F, the ethyl replaced by one or more-F, the propyl group replaced by one or more-F, the butyl replaced by one or more-F, the amyl group replaced by one or more-F or the hexyl replaced by one or more-F.
Described ester solvent can be methyl acetate, ethyl acetate, n-propyl acetate, methyl propionate, ethyl propionate, gamma-butyrolacton, decalactone, valerolactone, mevalonolactone, caprolactone, butyrate or capronate, but is not limited thereto.
Described ether solvents can be dibutyl ethers, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, dimethoxy-ethane, 2-methyltetrahydrofuran or oxolane, but is not limited thereto.
Described ketone solvent can be cyclohexanone, but is not limited thereto.
Described alcoholic solvent can be ethanol or isopropyl alcohol, but is not limited thereto.
Described aprotic solvent can be: nitrile is R-CN such as, and wherein R is based on straight chain, side chain or ring-type C
2-C
20the part of hydrocarbon and double bond, aromatic ring or ehter bond can be comprised; Acid amides is dimethyl formamide such as; Dioxolanes is DOX such as; Or sulfolane; But be not limited thereto.
Described non-aqueous organic solvent can be used alone or combinationally using with at least two kinds of different solvents.Such as, described non-aqueous organic solvent can be and is selected from a kind of solvent of above-mentioned carbonate solvent or the mixture of at least two kinds of solvents.If described non-aqueous organic solvent is the mixture of at least two kinds of solvents, then the mixing ratio of at least two kinds of solvents described in suitably can change according to the desired properties of lithium battery.
Such as, described non-aqueous organic solvent can be the mixture of EC, EMC and FEC, but is not limited thereto.
Lithium salts contained in described electrolyte is dissolved in the work playing lithium ion source in described non-aqueous organic solvent and in lithium battery and runs in order to make lithium battery, and accelerates lithium ion migration between a positive electrode and a negative electrode.
Such as, described lithium salts can be and is selected from following at least one supporting electrolyte salt: LiPF
6, LiBF
4, LiSbF
6, LiAsF
6, LiN (SO
2c
2f
5)
2, Li (CF
3sO
2) 2N (LiTFSI), LiC
4f
9sO
3, LiClO
4, LiAlO
2, LiAlCl
4, LiN (C
xf
2x+1sO
2) (C
yf
2y+ 1SO
2) (wherein x and y is natural number independently of one another), LiCl, LiI and LiB (C
2o
4)
2(two (oxalic acid) lithium borate (LiBOB)).
The concentration of described lithium salts can be about 0.1M ~ about 2.0M, such as about 0.6M ~ about 2.0M.If the concentration of lithium salts is in above-mentioned scope, then electrolyte can have required conductivity and viscosity, and lithium ion therefore can be made effectively to move.
Electrolyte can comprise the additive of cryogenic property and the lithium battery swelling behavior at high temperature that can improve lithium battery further.Such as, described additive can be: vinylene carbonate (VC); Have and be selected from halogen atom (such as ,-F ,-Cl ,-Br and-I), cyano group (CN) and nitro (NO
2) at least one substituent VC derivative; Vinyl ethylene carbonate (VEC); Have and be selected from halogen atom (such as ,-F ,-Cl ,-Br and-I), cyano group (CN) and nitro (NO
2) at least one substituent VEC derivative; Succinonitrile (SN); Succinyl oxide (SA); With propane sultone (PS); But be not limited thereto.
Described additive can be used alone or combinationally using with at least two kinds of different materials.
The amount of described additive can be about 0.1 weight portion ~ about 10 weight portions, based on the electrolyte of 100 weight portions.If the amount of additive is in above-mentioned scope, then the cryogenic property of lithium battery and lithium battery swelling character at high temperature can be improved to the level of expectation, and do not have the non-flame properties reduction of lithium battery.
Such as, the amount of additive can be about 1 weight portion ~ about 5 weight portions (or 1 weight portion ~ 5 weight portion) or about 3 weight portions ~ about 4 weight portions (or 3 weight portion ~ 4 weight portions), based on the electrolyte of 100 weight portions, but is not limited thereto.
Such as, the amount of additive can be 3 weight portions or 4 weight portions, based on the electrolyte of 100 weight portions, but is not limited thereto.
According to another embodiment of the present invention, lithium battery comprises: the positive pole comprising positive electrode active materials; Comprise the negative pole of negative active core-shell material; And electrolyte, the second compound that wherein said electrolyte comprises non-aqueous organic solvent, lithium salts, the first compound represented by formula 1 and represented by formula 2.Non-aqueous organic solvent, lithium salts, the first compound and the second compound contained in described electrolyte are carrying out describing more fully above.And described electrolyte can comprise additive further.Described additive is carrying out describing more fully above.
The type of lithium battery does not limit, and can be such as: lithium secondary battery, such as lithium ion battery, lithium ion polymer battery, lithium-sulfur cell etc.; Or lithium primary battery.
The positive electrode active materials that positive pole can comprise collector and arrange on a current collector.Positive pole can be prepared according to following methods.Can by positive electrode active materials, adhesive and solvent with the composition of preparation containing positive electrode active materials.Then, the composition that this can be contained positive electrode active materials is directly coated on the upper and drying of collector (such as, aluminium (Al) collector) to form anode active material layer, thus prepares positive plate.Or, this composition containing positive electrode active materials curtain coating on independent carrier can be made, and by the rete pressure be separated from it on a current collector to form anode active material layer, thus prepare positive plate.Prepare positive pole by any suitable method, and therefore the present invention is not limited thereto.Described solvent can be 1-METHYLPYRROLIDONE, acetone, water etc., but is not limited thereto.
Allow that the compound (inlaid scheme of lithiumation) of the reversible embedding of lithium ion and deintercalation can be used as positive electrode active materials.The example of positive electrode active materials can comprise the compound represented by any one in following formula, but is not limited thereto.
Li
aa
1-bx
bd
2(wherein 0.95≤a≤1.1 and 0≤b≤0.5); Li
ae
1-bx
bo
2-cd
c(wherein 0.95≤a≤1.1,0≤b≤0.5 and 0≤c≤0.05); LiE
2-bx
bo
4-cd
c(wherein 0≤b≤0.5 and 0≤c≤0.05); Li
ani
1-b-cco
bb
cd
α(wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0 < α≤2); Li
ani
1-b-cco
bx
co
2-αm
α(wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0 < α < 2); Li
ani
1-b-cco
bx
co
2-αm2 (wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0 < α < 2); Li
ani
1-b-cmn
bx
cd
α(wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0 < α≤2); Li
ani
1-b-cmn
bx
co
2-αm
α(wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0 < α < 2); Li
ani
1-b-cmn
bx
co
2-αm
2(wherein 0.95≤a≤1.1,0≤b≤0.5,0≤c≤0.05 and 0 < α < 2); Li
ani
be
cg
do
2(wherein 0.90≤a≤1.1,0≤b≤0.9,0≤c≤0.5 and 0.001≤d≤0.1); Li
ani
bco
cmn
dg
eo
2(wherein 0.90≤a≤1.1,0≤b≤0.9,0≤c≤0.5,0≤d≤0.5 and 0.001≤e≤0.1); Li
aniG
bo
2(wherein 0.90≤a≤1.1 and 0.001≤b≤0.1); Li
acoG
bo
2(wherein 0.90≤a≤1.1 and 0.001≤b≤0.1); Li
amnG
bo
2(wherein 0.90≤a≤1.1 and 0.001≤b≤0.1); Li
amn
2g
bo
4(wherein 0.90≤a≤1.1 and 0.001≤b≤0.1); QO
2; QS
2; LiQS
2; V
2o
5; LiV
2o
5; LiZO
2; LiNiVO
4; Li
(3-f)j
2(PO
4)
3(wherein 0≤f≤2); Li
(3-f)fe
2(PO
4)
3(wherein 0≤f≤2); And LiFePO
4.
In above formula, A is selected from nickel (Ni), cobalt (Co), manganese (Mn) and combination thereof; X is selected from aluminium (Al), nickel (Ni), cobalt (Co), manganese (Mn), chromium (Cr), iron (Fe), magnesium (Mg), strontium (Sr), vanadium (V), rare earth element and combination thereof; D is selected from oxygen (O), fluorine (F), sulphur (S), phosphorus (P) and combination thereof; E is selected from cobalt (Co), manganese (Mn) and combination thereof; M is selected from fluorine (F), sulphur (S), phosphorus (P) and combination thereof; G is selected from aluminium (Al), chromium (Cr), manganese (Mn), iron (Fe), magnesium (Mg), lanthanum (La), cerium (Ce), strontium (Sr), vanadium (V) and combination thereof; Q is selected from titanium (Ti), molybdenum (Mo), manganese (Mn) and combination thereof; Z is selected from chromium (Cr), vanadium (V), iron (Fe), scandium (Sc), yttrium (Y) and combination thereof; Vanadium (V), chromium (Cr), manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu) and combination thereof is selected from J.
Surface coating layer can be formed on these compounds.Or, the mixture of the compound it without coating layer and the compound it with coating layer can be used.Described coating layer can comprise at least one compound of coated element, and it is selected from the oxide of described coated element, hydroxide, oxyhydroxide, carbonic acid oxonium salt (oxycarbonate) and hydroxyl carbonate (hydroxycarbonate).Compound for described coating layer can be unbodied or crystallization.Coated element contained in described coating layer can be magnesium (Mg), aluminium (Al), cobalt (Co), potassium (K), sodium (Na), calcium (Ca), silicon (Si), titanium (Ti), vanadium (V), tin (Sn), germanium (Ge), gallium (Ga), boron (B), arsenic (As), zirconium (Zr) or its mixture.
When using the compound of so coated element, can use any not to the method such as formation such as spraying process, the infusion process coating layer that the physical property of positive electrode active materials has a negative impact.
Such as, positive electrode active materials can by formula LiNi
0.5co
0.2mn
0.3o
2and/or LiCoO
2represent, but be not limited thereto.
Adhesive contained in anode active material layer plays and positive electrode active materials particle is bonded together securely and makes the effect of positive electrode active materials particle and collector good bond.The example of adhesive comprises; but be not limited to, the SBR of the polyvinyl chloride of polyvinyl alcohol, carboxymethyl cellulose, hydroxypropyl cellulose, diacetyl cellulose, polyvinyl chloride, carboxylation, polyvinyl fluoride, the polymer with ethylene oxide repeating units, polyvinylpyrrolidone, polyurethane, polytetrafluoroethylene, Kynoar, polyethylene, polypropylene, butadiene-styrene rubber (SBR), propylene acidifying, epoxy resin and nylon.
Anode active material layer can comprise conductive agent further.Conductive agent is used for providing conductivity for positive pole.Any electric conducting material not causing chemical change in the battery can be used.The example of described conductive agent can comprise: carbonaceous material, such as native graphite, Delanium, carbon black, acetylene black, Ketjen black, carbon fiber etc.; The material based on metal of powder or fibers form, such as copper (Cu), nickel (Ni), aluminium (Al), silver (Ag) etc.; And electric conducting material, comprise conducting polymer, such as polyphenylene derivatives; And composition thereof.
Collector can be aluminium (Al), but is not limited thereto.
Similarly, can by negative active core-shell material, conductive agent, adhesive and solvent with the composition of preparation containing negative active core-shell material.The described composition containing negative active core-shell material can directly be coated on collector (such as, Cu collector), or can on independent carrier curtain coating and the negative active core-shell material rete be separated from it can being pressed on Cu collector to obtain negative plate.In this, the amount of negative active core-shell material, conductive agent, adhesive and solvent to can be in lithium battery conventional those.
Native graphite, Delanium, silicon/carbon complex, silicon metal, silicon thin film, lithium metal, lithium alloy, carbonaceous material or graphite can be used as negative active core-shell material.Conductive agent, adhesive and solvent in the described composition containing negative active core-shell material can be identical containing those in the composition of positive electrode active materials with described.If needed, can further to described composition containing positive electrode active materials with describedly add plasticizer to produce hole in battery lead plate containing in the composition of negative electrode active material.
According to the type of lithium battery, dividing plate can be inserted between a positive electrode and a negative electrode.Any dividing plate being generally used for lithium battery can be used.In one embodiment, dividing plate can have the lower resistance for the Ion transfer in electrolyte and have high electrolyte retention.Example for the formation of the material of dividing plate comprises glass fibre, polyester, Teflon, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and combination thereof, and it can be adhesive-bonded fabric or yarn fabric separately.The dividing plate reeled formed by such as polyethylene and polyacrylic material can be used for lithium ion battery.The dividing plate of a large amount of organic bath can be kept to can be used for lithium ion polymer battery.These dividing plates can according to following methods manufacture.
By fluoropolymer resin, filler and solvent to prepare baffle combination thing.Then, this baffle combination thing directly can be coated on electrode, then dry to form separator membrane.Or, this baffle combination thing can on independent carrier curtain coating, then dry to form baffle combination thing film, and the baffle combination thing rete be separated from carrier can be pressed on electrode to form separator membrane.
Described fluoropolymer resin can be any material used usually used as the adhesive for battery lead plate.The example of described fluoropolymer resin comprise vinylidene/hexafluoropropylene copolymer, Kynoar, polyacrylonitrile, polymethyl methacrylate, and composition thereof.Such as, the vinylidene/hexafluoropropylene copolymer with about 8 ~ about 25 % by weight (or having 8 ~ 25 % by weight) hexafluoropropylene can be used.
Dividing plate can be inserted to form battery component between positive plate and negative plate.By described battery component winding or folding, be then sealed in cylindrical or rectangular battery shell.Then, in battery case, electrolyte is injected to complete the manufacture of lithium ion battery.Or, according to an embodiment of the invention, multiple electrode assemblie can two unit (bi-cell) structure stacked and use electrolyte-impregnated.Gains put into bag and seals, thus completing the manufacture of lithium ion polymer battery.
Fig. 1 is the perspective schematic view of the lithium battery 30 according to embodiment of the present invention.With reference to Fig. 1, the lithium battery 30 according to this execution mode comprises: positive pole 23, negative pole 22, insert the dividing plate 24 between positive pole 23 and negative pole 22, be impregnated into the electrolyte in positive pole 23, negative pole 22 and dividing plate 24, battery case 25, and the seal member 26 of sealed cell shell 25.Lithium battery 30 is manufactured by the following: going up stacked each other by positive pole 23, dividing plate 24, negative pole 22 and dividing plate 24, reel this lamination in a spiral form, and be inserted in battery case 25 by the lamination of this winding.
Existence and/or the amount of target component (such as, the first compound and the second compound) contained in the electrolyte of lithium battery to be analyzed record by gas-chromatography (GC)/mass spectrum (MS).
In this, the quantitative analysis of target component can use internal standard method (ISTD) and/or external standard method (ESTD) to carry out.
According to ISTD, ethyl acetate (EA) can be used to carry out quantitative analysis as internal standard compound.According to ESTD, for each concentration of target component (such as, the first compound and the second compound) to be analyzed, at least one reference material can be used to carry out quantitative analysis.
Such as, can comprise the method that target component (such as, the first compound and the second compound) contained in the electrolyte of lithium battery carries out quantitative analysis: extract electrolyte from lithium battery; Carry out GC/MS by using ISTD or ESTD to extracted electrolyte to analyze with the data gathering target component; With the amount (such as, % by weight or volume %) being calculated target component by these data, but described method is not limited thereto.
At " Principles of Instrumental Analysis ", the 5th edition, Douglas A.Skoog etc., disclose the details that GC/MS analyzes, are incorporated herein by reference by the full content of the document in 701-722 page.
Can set for automatic integration reference condition using detect initial peak width from the spectrogram obtained as the result analyzed electrolytical GC/MS and be 0.004 or higher and peak threshold value (peak threshold) be 8 or higher peak.Then, as the result of automatic integration, the first compound can be about 0.1 ~ about 2 (or 0.1 ~ 2) with the ratio of the peak area of the second compound.Describe GC/MS analytical method and result more fully in the examples below.
Hereinafter, with reference to following examples, one or more execution mode of the present invention is described in more detail.But these embodiments are not intended to limit the scope of one or more execution mode of the present invention.
Embodiment
Embodiment 1
Native graphite, butadiene-styrene rubber (SBR) and carboxymethyl cellulose (CMC) weight ratio using 97.5: 1: 1.5 is being mixed to prepare cathode size in the 1-METHYLPYRROLIDONE of solvent.Be coated on by this cathode size to form thin negative plate on copper (Cu) paper tinsel (), by its dry 3 hours or longer time at 135 DEG C, and compacting is to manufacture the negative pole comprising the negative electrode active layer with 60 μm of thickness.
Using the LiCoO as positive electrode active materials
2, carbon conductor and the weight ratio of Kynoar (PVDF) using 96: 2: 2 as adhesive be dispersed in the 1-METHYLPYRROLIDONE of solvent to prepare anode sizing agent.This anode sizing agent is coated on aluminium (Al) paper tinsel (12 μm) to form the thin positive plate with 60 μm of thickness, by its dry 3 hours or longer time at 135 DEG C, and compacting is to manufacture the positive pole comprising the positive-active layer with 60 μm of thickness.
Be the ethylene carbonate (EC) of 20: 5: 50: 20: 5, carbonic acid PVF ester (FEC), methyl ethyl carbonate (EMC), compound 1a (CF as the first compound using volume ratio
2h-CF
2-CH
2-O-CF
2-CF
2h, fluorine atom/hydrogen atom=2) and (represented by formula 2, wherein R as the compound 2a of the second compound
1~ R
5for-F and R
6for-OCH
2cH
3) mixture and 0.5M LiPF
6, 0.5M LiTFSI and 0.4%LiBF
4mixing is to prepare electrolyte.
Use porous polyethylene (PE) film (having 18 μm of thickness) as dividing plate winding negative pole and positive pole, and suppressed and put into battery case.Then, in battery case, inject described electrolyte to manufacture square lithium secondary battery, thus manufacture the lithium battery with 1200mAh capacity.
Embodiment 2
Manufacture lithium battery in the same manner as in example 1, except the volume ratio of EC, FEC, EMC, compound 1a and compound 2a being adjusted to except 20: 5: 45: 20: 10.
Embodiment 3
Manufacture lithium battery in the same manner as in example 1, except the volume ratio of EC, FEC, EMC, compound 1a and compound 2a being adjusted to except 20: 5: 45: 25: 5.
Embodiment 4
Manufacture lithium battery in the same manner as in example 1, except using by wherein R
1, R
2, R
4and R
5for-F and R
3and R
6for-OCH
2cH
3the compound 2b that represents of formula 2 replace compound 2a as the second compound and the volume ratio of EC, FEC, EMC, compound 1a and compound 2b be adjusted to outside 20: 5: 50: 20: 5.
Embodiment 5
Lithium battery is manufactured, except the volume ratio of EC, FEC, EMC, compound 1a and compound 2b being adjusted to except 20: 5: 45: 20: 10 in mode in the same manner as in Example 4.
Embodiment 6
Lithium battery is manufactured, except the volume ratio of EC, FEC, EMC, compound 1a and compound 2b being adjusted to except 20: 5: 45: 25: 5 in mode in the same manner as in Example 4.
Comparative example 1
Manufacture lithium battery in the same manner as in example 1, except not adding compound 2a and the volume ratio of EC, FEC, EMC and compound 1a being adjusted to except 20: 5: 55: 20.
Comparative example 2
Manufacture lithium battery in the same manner as in example 1, except not adding compound 1a and the volume ratio of EC, FEC, EMC and compound 2a being adjusted to except 20: 5: 55: 20.
Comparative example 3
Lithium battery is manufactured, except not adding compound 1a and the volume ratio of EC, FEC, EMC and compound 2b being adjusted to except 20: 5: 55: 20 in mode in the same manner as in Example 4.
Evaluation operation example 1: capacity and puncture properties evaluation
The lithium battery manufactured according to embodiment 1 ~ 6 and comparative example 1 ~ 3 is at room temperature charged under the cut-off current of 20mA with the constant voltage (CV) of the constant current of 0.2C (CC) and 4.2V.Then, battery is discharged under the cut-ff voltage of 2.75V with the electric current of 520mA.Lithium battery is made to experience formation process.
According to the lithium battery of embodiment 1 ~ 6 and comparative example 1 ~ 3 after experience formation process, with charging under the cut-off current of the CV of CC and 4.2V of 0.5C at 0.1C 10 minutes under room temperature (about 25 DEG C).Then, battery discharges 10 minutes under the cut-ff voltage of 2.75V with the electric current of 0.2mA.Measure the capacity of lithium battery, and result is shown in Table 1.
According to the lithium battery of embodiment 1 ~ 6 and comparative example 1 ~ 3 under room temperature (about 25 DEG C) to charge under the cut-off current of the CV of CC and 4.35V of 0.5C at 0.1C.Then, the nail with 5mm diameter is made to penetrate lithium battery with the speed of 40mm/s.Evaluate the puncture properties of lithium battery, and result is shown in Table 1.
Table 1
| First compound | Second compound | Capacity (mAh) | Puncture experimental result | |
| Embodiment 1 | Compound 1a | Compound 2a | 1262 | Not on fire |
| Embodiment 2 | Compound 1a | Compound 2a | 1259 | Not on fire |
| Embodiment 3 | Compound 1a | Compound 2a | 1259 | Not on fire |
| Embodiment 4 | Compound 1a | Compound 2b | 1262 | Not on fire |
| Embodiment 5 | Compound 1a | Compound 2b | 1261 | Not on fire |
| Embodiment 6 | Compound 1a | Compound 2b | 1262 | Not on fire |
| Comparative example 1 | Compound 1a | - | 1262 | Blast |
| Comparative example 2 | - | Compound 2a | 1267 | On fire |
| Comparative example 3 | - | Compound 2b | 1266 | On fire |
With reference to table 1, when evaluating the puncture properties of lithium battery, different from according to the lithium battery of comparative example 1 ~ 3, on fire according to both not occurred in the lithium battery of embodiment 1 ~ 6 that blast did not occur yet, show that the lithium battery of embodiment 1 ~ 6 is high safeties.
Evaluation operation example 2: electrolytical component analysis
Carry out GC/MS to compound 1a, compound 2a and compound 2b respectively with following condition to analyze with the peak position of deterministic compound 1a, 2a and 2b, as shown in Figure 2,3 and 4:
Furnace temperature appreciation condition: 40 DEG C (1 minute)-15 DEG C/min-300 DEG C (2 minutes)
Inlet temperature: 250 DEG C
Inlet distribution compares: 1/50
Pillar: HP-5MS
Column flow rate: 1ml/ minute
MS source: Quadropole
MS scope: 30-600
The equipment analyzed for GC/MS is the GC-6890/Inert5973 that Agilent manufactures.
Then, disassemble that the electrolyte of each lithium battery is sampled by according to the lithium battery of embodiment 1,2,4 and 5.Then, to carry out GC/MS analysis with condition identical above to sampled electrolyte.Result is shown in Fig. 5 A and 5B (embodiment 1), Fig. 6 A and 6B (embodiment 2), Fig. 7 A and 7B (embodiment 4) and Fig. 8 A and 8B (embodiment 5).Setting is used for the reference condition of automatic integration and is 0.004 or higher with the initial peak width detected in each electrolytical GC/MS analysis of spectra and peak threshold value is the peak of 8 or higher.Then, automatic integration is carried out to calculate the ratio of the peak area of the first compound (that is, compound 1a) and the second compound (compound 2a or 2b).Result is shown in Table 2.
Table 2
1: parts by volume, based on the cumulative volume of EC, the FEC of 100 parts by volume, EMC, the first compound and the second compound
The result that the electrolytical GC/MS of the lithium battery according to embodiment 1,2,4 and 5 is analyzed can be confirmed by table 2.
As mentioned above, one or more according to the above execution mode of the present invention, described electrolyte can keep its electrical characteristics such as high power capacity and have excellent noninflammability.Therefore, to comprise described electrolytical lithium battery and can be high safety.
Although invention has been described to have combined some illustrative embodiments, but should understand and the invention is not restricted to disclosed execution mode, but contrary, its intention contain be included in claims and its equivalent spirit and scope in various improvement and equivalent combinations.
Claims (10)
1., for the electrolyte of lithium battery, comprising:
Non-aqueous organic solvent, lithium salts, the first compound represented by following formula 1 and the second compound represented by following formula 2:
Formula 1
Q
1-O-Q
2
Formula 2
Wherein,
Q
1for the C replaced by one or more-F
2-C
30alkyl;
Q
2for C
1-C
30alkyl, C
2-C
30thiazolinyl, C
2-C
30alkynyl, the C replaced by one or more-F
1-C
30alkyl, the C replaced by one or more-F
2-C
30thiazolinyl or the C replaced by one or more-F
2-C
30alkynyl;
R in described second compound
1~ R
6be selected from-F and-OT independently of one another
1, wherein T
1for: C
1-C
30alkyl; C
2-C
30thiazolinyl; C
2-C
30alkynyl; C
6-C
12cycloalkyl; C
6-C
30aryl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
1-C
30alkyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
30thiazolinyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
2-C
30alkynyl; The C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
12cycloalkyl; Or the C that at least one substituting group being selected from-F, hydroxyl and carboxyl replaces
6-C
30aryl, wherein gets rid of wherein R
1~ R
6be all-F or-OT
1situation, and the number ratio of fluorine atom in described first compound and hydrogen atom is 1 or higher,
The amount of wherein said first compound is 10 parts by volume ~ 25 parts by volume, based on the cumulative volume of the described non-aqueous organic solvent of 100 parts by volume, described first compound and described second compound,
The amount of wherein said second compound is 5 parts by volume ~ 10 parts by volume, based on the cumulative volume of the described non-aqueous organic solvent of 100 parts by volume, described first compound and described second compound.
2. the electrolyte for lithium battery of claim 1, the Q in wherein said first compound
1and Q
2be by the ethyl of one or more-F replacement, by the propyl group of one or more-F replacement, by the butyl of one or more-F replacement, by the amyl group of one or more-F replacement, by the hexyl of one or more-F replacement, by the heptyl of one or more-F replacement or by the octyl group of one or more-F replacement independently of one another.
3. the electrolyte for lithium battery of claim 1, the Q in wherein said first compound
1and Q
2be selected from-CF independently of one another
2-CF
2h ,-CH
2-CF
2-CF
2h ,-CF
2-CF
3,-CH
2-CF
2-CF
3,-CF
2-CFH
2with-CH
2-CF
2-CFH
2.
4. the electrolyte for lithium battery of claim 1, the fluorine atom in wherein said first compound and the number ratio of hydrogen atom are 1 ~ 10.
5. the electrolyte for lithium battery of claim 1, wherein in described second compound, R
1~ R
5for-F and R
6for-OT
1; Or wherein in described second compound, R
1, R
2, R
4and R
5for-F and R
3and R
6for-OT
1.
6. the electrolyte for lithium battery of claim 1, wherein T
1for methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, the methyl replaced by one or more-F, the ethyl replaced by one or more-F, the propyl group replaced by one or more-F, the butyl replaced by one or more-F, the amyl group replaced by one or more-F, the hexyl replaced by one or more-F, the heptyl replaced by one or more-F or the octyl group replaced by one or more-F.
7. the electrolyte for lithium battery of claim 1, wherein said non-aqueous organic solvent comprises at least one carbonate solvent being selected from carbonate material, described carbonate material carrys out the group of freely following composition: dimethyl carbonate (DMC), diethyl carbonate (DEC), dipropyl carbonate (DPC), methyl propyl carbonate (MPC), ethyl propyl carbonic acid ester (EPC), methyl ethyl carbonate (EMC), ethylene carbonate (EC), propene carbonate (PC), butylene (BC), and the derivative that their hydrogen is replaced by one or more-F.
8. the electrolyte for lithium battery of claim 1, comprises further and is selected from following additive: vinylene carbonate (VC); Have and be selected from halogen atom, cyano group (CN) and nitro (NO
2) at least one substituent VC derivative; Vinyl ethylene carbonate (VEC); Have and be selected from halogen atom, cyano group (CN) and nitro (NO
2) at least one substituent VEC derivative; Succinonitrile (SN); Succinyl oxide (SA); With propane sultone (PS).
9. the electrolyte for lithium battery of claim 1, wherein in the spectrogram obtained by the analysis of gas-chromatography (GC)/mass spectrum (MS), described first compound is 0.1 ~ 2 with the ratio of the peak area of described second compound.
10. lithium battery, comprising:
Comprise the negative pole of negative active core-shell material;
Comprise the positive pole of positive electrode active materials; With
The electrolyte for lithium battery of any one of claim 1-9.
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| KR1020090112197A KR101117699B1 (en) | 2009-11-19 | 2009-11-19 | Electrolytic solution for lithium battery and lithium battery employing the same |
| KR112197/09 | 2009-11-19 |
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2009
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2010
- 2010-09-03 US US12/875,872 patent/US8524401B2/en active Active
- 2010-11-17 JP JP2010256515A patent/JP5202607B2/en active Active
- 2010-11-17 EP EP10251948.5A patent/EP2325936B1/en active Active
- 2010-11-19 CN CN201010558114.XA patent/CN102074737B/en active Active
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| US7476468B1 (en) * | 2005-11-10 | 2009-01-13 | Quallion Llc | Flame retardant battery |
| CN101490893A (en) * | 2006-07-13 | 2009-07-22 | 大金工业株式会社 | Electrochemical device |
Also Published As
| Publication number | Publication date |
|---|---|
| US20110117443A1 (en) | 2011-05-19 |
| CN102074737A (en) | 2011-05-25 |
| US8524401B2 (en) | 2013-09-03 |
| JP2011108649A (en) | 2011-06-02 |
| EP2325936A1 (en) | 2011-05-25 |
| KR101117699B1 (en) | 2012-02-24 |
| JP5202607B2 (en) | 2013-06-05 |
| EP2325936B1 (en) | 2016-01-13 |
| KR20110055253A (en) | 2011-05-25 |
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